1-Hydroxymethyl-2-acyl cyclopropane derivatives and esters thereof

ABSTRACT

Described are 1-hydroxymethyl-2-acyl cyclopropane derivatives having one of the structures:   &lt;IMAGE&gt;    &lt;IMAGE&gt;  +TR  &lt;IMAGE&gt;  and utilities thereof for their organoleptic properties.

This is a divisional of application Ser. No. 422,486, filed 9/23/82,U.S. Pat. No. 4,435,428.

BACKGROUND OF THE INVENTION

The instant invention is directed to 1-hydroxymethyl-2-acyl cyclopropanederivatives having the generic structure: ##STR2## wherein Z representshydrogen, acyl having the structure: ##STR3## and substituted oxyacylhaving the structure: ##STR4## and cyclic condensation products thereofhaving the structure: ##STR5## wherein R₁, R₂ and R₃ represent C₁ -C₁₀alkyl; wherein R₁ ' is C₁ -C₁₀ alkylidene; and wherein R₄, R₅, R₆ and R₇represent hydrogen or C₁ -C₃ lower alkyl,

processes for preparing same involving the reaction of halo methyloxirane derivatives defined according to the structure: ##STR6## whereinX represents chloro, bromo or iodo with substituted 1,3-propanedioneshaving the structure: ##STR7## and organoleptic uses thereof inaugmenting or enhancing the aroma or taste of consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (or alter, modify or enhance) flavors andfragrances to (or in) various consumable materials. These substances areused to diminish the use of natural materials, some of which may be inshort supply and to provide more uniform properties in the finishedproduct.

Sweet, green, herbaceous, fruity, pineapple, grapefruit-like, leathery,coconut-like, and jasmine-like aromas with mushroom-like and anisicundertones are particularly desirable in several types of perfumecompositions and for use in perfumed articles and colognes.

Sweet, fruity, fresh pineapple-like, fresh grapefruit-like, coconut-likeand mushroom-like aroma and taste nuances are particularly desirable formany uses in foodstuff flavors, particularly tropical fruit flavors.

Compounds containing carbonyl functions and cyclopropyl moieties areknown for use in the art of perfumery and flavors. Thus, substitutedcyclopropane derivatives such as ethylchrysanthemumate(2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylic acid, ethyl ester) having the structure: ##STR8## isdisclosed as Compound 487 in "Perfume and Flavor Chemicals (AromaChemicals)" Volume 1, Arctander published 1969 as having a powerful,winey, herbaceous, sweet and ethereal, very pleasant odor of intriguingcomplexity. Arctander states that this material has spicy-herbaceous,warm and almost green-floral notes which resemble certain notes in ajasmine complex. However, no indication exists that this type ofcompound augments or enhances the nuances stated in the instantapplication.

Furthermore, U.S. Pat. No. 3,926,860 issued on Dec. 16, 1975 (thedisclosure of which is incorporated by reference herein) states that asa result of analyzing natural patchouli oil, it was found thatcis-2-n-pentylcyclopropane-1-carboxylic acid having the structure:##STR9## is a key component for patchouli fragrance having apatchouli-like, animal, leathery note and having the capability ofimparting such notes to perfumes and cosmetic compositions. The compoundhaving the structure: ##STR10## is indicated to have fragranceproperties which are surprisingly different in kind from other knowncompounds and compositions in the "prior art", to wit:

i. Beilstein, Volume E III 9, page 101 disclosing2-n-hexyl-cyclopropane-carboxylic acid-(1) (no disclosure of aroma);

ii. Snejkal et al., Collection Czech. Chem. Communications 25, 1746-50(1960) discloses interalia, cis-isobutyl cyclopropane carboxylic acid(no disclosure of aroma);

iii. Danilkina and D'yakonov, Zh. Obshch. Khin., 34 (9) 3129-30 (1964)discloses 2-butyl cyclopropane carboxylic acid (cis/trans mixture withno aroma disclosed);

iv. Dolgii et al., Farmakol. Toksikol. 30(2), 199-203 (1967) discloses2-n-pentylcyclopropane carboxylic acid (no reference made to isomericconfiguration of to aroma);

v. D'yakonov et al., Zh. Obschei. Khim. 35, 2169 (1965) disclosesmixtures of cis and trans-2-pentylcyclopropane carboxylic acid, thetrans acid being in the major proportion. No reference is made to aroma;

vi. Julia et al. Bull Soc. Chim. France 1970, 1805 disclosescis-2-n-butyl cyclopropane carboxylic acid ethyl ester at page 1808without reference being made to its aroma.

The 1-hydroxymethyl-2-acyl cyclopropane derivatives of the instantinvention have chemical structures and properties different in kind fromthe chemical structures and properties of the compounds of the priorart.

Furthermore, the processes for producing the 1-hydroxymethyl-2-acylcyclopropane derivatives of our invention are novel. Organic Synthesis,Volume IV, John Wiley & Sons Publishing Company, 1969 at page 597discloses a technique for making acyl cyclopropane derivatives accordingto the reaction sequence: ##STR11## but the mechanism of our inventionis neither expressly nor implicitly set forth therein.

Indeed, the prior art teaches away from our invention as is seen byMesropyan et al. at Chem. Abstracts, Volume 78, 1973, 135590y whichteaches the reaction: ##STR12## and further, as seen by Arbuzov et al.Volume 80, 1974, Chem. Abstracts 47884h which teaches the reaction:##STR13##

Indeed, no rearrangement of the cyclopropyl moiety occurs when reactingthe epichlorohydrin with a difunctional moiety as is shown in thereaction: ##STR14## disclosed in Chem. Abstracts 137316n, Volume 78,1973 (abstract of South African Pat. No. 7107,767).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example Icontaining the compounds having the structures: ##STR15## wherein Y₁ andY₂ are the same or different and each represents chloro or hydroxyl.

FIG. 1A is the GLC profile for the distillation product of the reactionproduct of Example I containing the compounds having the structures:##STR16##

FIG. 2 is the NMR spectrum for the peak indicated by reference numeral"10" in FIG. 1 which is for the compound having the structure: ##STR17##(Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 3 is the infra-red spectrum for the compound of the peak indicatedby reference numeral "10" of FIG. 1 having the structure: ##STR18##

FIG. 3A is the NMR spectrum for the peak indicated by reference numeral"12" on FIG. 1A for the compound having the structure: ##STR19##(Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 3B is the IR spectrum for the peak indicated by reference numeral"12" on FIG. 1A which is for the compound having the structure:##STR20##

FIG. 4 is the GLC profile for the reaction product of Example IIcontaining the compound having the structure: ##STR21##

FIG. 5 is the NMR spectrum for the peak indicated by reference numeral"40" on the GLC profile of FIG. 4 for the compound having the structure:##STR22## (Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 6 is the infra-red spectrum for the peak indicated by referencenumeral "40" on the GLC profile of FIG. 4 for the compound having thestructure: ##STR23##

FIG. 7 is the GLC profile for the reaction product of Example IIIcontaining the compound having the structure: ##STR24##

FIG. 8 is the NMR spectrum for the peak indicated by reference numeral"70" on FIG. 7, having the structure: ##STR25## (Solvent: CFCl₃ ; Fieldstrength: 100 MHz).

FIG. 9 is the infra-red spectrum for the peak indicated by referencenumeral "70" on FIG. 7 for the compound having the structure: ##STR26##

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example I(conditions: 10% SF-96 column, 6'×0.25" programmed at 100°-220° C. at 8°C. per minute). The peak indicated by reference numeral "10" is the peakfor the compounds defined according to the structure: ##STR27## whereinY₁ and Y₂ are the same or different and each represents chloro orhydroxyl. The peak indicated by reference numeral "11" is the peak forthe compound defined according to the structure: ##STR28##

FIG. 1A is the GLC profile for the spinning band distillation product ofthe reaction product of Example I (conditions: 8'×1/4" 10% SF-96 columnprogrammed at 100°-220° C. at 8° C. per minute). The peak indicated byreference numeral "12" is the peak for the compound having thestructure: ##STR29## The peak indicated by reference numeral "13" is thepeak for the compound having the structure: ##STR30##

FIG. 4 is the GLC profile for the reaction product of Example IIcontaining the compound having the structure: ##STR31## The peakindicated by reference numeral "40" is the peak for the compound havingthe structure: ##STR32## The GLC conditions are: 10% SF-96 column,6'×0.25", programmed at 100°-220° C. at 8° C. per minute.

FIG. 7 is the GLC profile for the reaction product of Example III.Conditions: 10% SF-96 column, 6'×0.25" programmed at 100°-220° C. at 8°C. per minute. The peak indicated by reference numeral "70" is the peakfor the compound having the structure: ##STR33##

THE INVENTION

It has now been discovered that novel solid and liquid foodstuffs,chewing gums, medicinal products, toothpastes, chewing tobaccos andflavoring compositions therefor having sweet, fruity, pineapple,grapefruit-like, coconut-like and mushroom aroma and tastecharacteristics, and novel perfume compositions, colognes and perfumedarticles having sweet, green, herbaceous, fruity, pineapple,grapefruit-like, leathery, coconut-like, jasmine-like and woody aromaswith mushroom-like and anisic-like undertones may be provided by1-hydroxymethyl-2-acyl cyclopropane derivatives defined according to thestructure: ##STR34## wherein Z represents hydrogen, acyl having thestructure: ##STR35## and substituted oxyacyl having the structure:##STR36## and condensation products thereof defined according to thestructure: ##STR37## wherein R₁, R₂ and R₃ represent C₁ -C₁₀ alkyl;wherein R₁ ' represents C₁ -C₁₀ alkylidene; and wherein R₄, R₅, R₆ andR₇ represent hydrogen or C₁ -C₃ lower alkyl.

Our invention contemplates various geometric and stereo isomers, forexample, the isomers defined according to the generic structure:##STR38## and other "cis" and "trans" isomers. The compounds definedaccording to the structure: ##STR39## and the compounds definedaccording to the structure: ##STR40## are indicative of mixtures of"cis" or "trans" isomers or individual "cis" or "trans" isomers.

The 1-hydroxymethyl-2-acyl cyclopropane derivatives of our invention maybe prepared according to a novel process of our invention by reacting ahalomethyloxirane having the structure: ##STR41## with a disubstitutedpropanedione having the structure: ##STR42## in the presence of analkali metal alkoxide to form an ester having the structure: ##STR43##This ester may be isolated and used "as is" for its organolepticproperties or it may be further hydrolyzed to form an alcohol having thestructure: ##STR44## This alcohol may be used "as is" for itsorganoleptic properties or it may be further reacted with a dialkylcarbonate having the structure: ##STR45## thereby forming the carbonatehaving the structure: ##STR46## which is isolated and used for itsorganoleptic properties; or this alcohol may be condensed according tothe reaction: ##STR47## by heating the alcohol and removing a moleculeof water to form the compound having the structure: ##STR48##

The reaction between the disubstituted propanedione and the halo methyloxirane derivative is shown according to the following scheme: ##STR49##

The reaction of the resulting ester with a hydrolysis agent is shownaccording to the following scheme: ##STR50##

In preparing the compound having the structure: ##STR51## and inpurifying same, at higher temperatures of distillation, these compoundswill self-condense thereby forming compounds defined according to thestructure: ##STR52## wherein R₁ ' is C₁ -C₁₀ alkylidene. If thedistillation is carried out at a very high temperature, high yields ofcompounds defined according to the structure: ##STR53## will be formed.These compounds are also useful for their aroma properties.

The reaction of the resulting alcohol with the dialkyl carbonate to formthe carbonate derivatives is shown according to the reaction: ##STR54##

The reaction mechanism to form the acetate using the alkali metalalkoxide is shown thusly: ##STR55##

In examining the foregoing mechanism, the first compound that is formedcan be depicted according to the structure: ##STR56## wherein the alkalimetal alkoxide, M, O, R" is involved in the formation of theintermediate wherein M represents alkali metal including lithium,potassium and sodium and R" is alkyl including ethyl, methyl, n-propyl,isopropyl, n-butyl, secondary butyl and t-butyl. The compound having thestructure: ##STR57## rearranges to form the compound having thestructure: ##STR58## which, in turn, rearranges to form the ester havingthe structure: ##STR59##

In place of the halomethyloxirane, equivalent compounds may be used, forexample, those defined according to the structure: ##STR60## oraccording to the structure: ##STR61## wherein X is halogen includingchloro, bromo and iodo and X₁ and X₂ are the same or different and eachrepresents chloro, bromo or iodo.

In carrying out the reaction between the substituted 1,3-propanedioneand the halo methyl oxirane or substitute therefor, the mole ratio ofepihalo oxirane:substituted propanedione may vary from 0.5:1 up to 1:0.5with a preferred mole ratio of halo methyl oxirane:substitutedpropanedione being about 1:1. The mole ratio of alkali metalalkoxide:substituted 1,3-propanedione may vary from about 3:1 down toabout 1:1 with a preferred mole ratio of alkali metalalkoxide:substituted 1,3-propanedione being about 2:1. The reactiontakes place in a non-reactive solvent and preferred solvents are methylalcohol, ethyl alcohol, n-propanol and isopropanol. The reactiontemperature may vary from about 70° C. up to about 120° C. and ispreferably carried out at reflux conditions. The reaction pressure mayvary from 0.5 atmospheres up to about 20 atmospheres but is mostconveniently 1 atmosphere. Accordingly, the reaction is preferred to becarried out at a temperature in the range of from about 65° C. up toabout 95° C. at atmospheric pressure. The time of reaction may vary fromabout 1 hour up to about 12 hours depending upon the temperature andpressure of reaction with higher temperatures of reaction giving rise toa lesser amount of required time of reaction to obtain the desiredyield. At the end of the reaction, the reaction product may be isolatedand fractionally distilled (in the event that it is desired to be usedfor its organoleptic properties). This product is the ester definedaccording to the structure: ##STR62## On the other hand, the resultingreaction product may be hydrolyzed without isolation, in situ in orderto form the alcohol defined according to the structure: ##STR63## Thehydrolysis is carried out at a temperature of from about 0° C. up toabout 100° C. with a preferred hydrolysis temperature of between 60° and85° C. using aqueous dilute mineral acid such as dilute hydrochloricacid, dilute sulfuric acid or dilute phosphoric acid. Preferably themineral acid is between 2% and 20% hydrochloric acid. In addition,aqueous solutions of salts which have a pH of between 0.5 and 3 may beused, e.g. aqueous ammonium chloride.

The resulting hydrolysis product having the structure: ##STR64## may beisolated from the reaction mass and fractionally distilled or it may befurther reacted after isolation from the reaction mass, with a dialkylcarbonate defined according to the structure: ##STR65##

Thus, the carbonates of our invention defined according to thestructure: ##STR66## are prepared by reaction of the compounds definedaccording to the structure: ##STR67## with the dialkyl carbonates havingthe structure: ##STR68## in the presence of an alkali metal alkoxidesuch as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassiummethoxide, potassium ethoxide and potassium t-butoxide. The reactionbetween the alcohol and the dialkyl carbonate takes place in the absenceof any additional solvent. The mole ratio range of dialkylcarbonate:alcohol may vary from about 3 moles dialkyl carbonate:0.5moles alcohol down to 1 mole dialkyl carbonate:1 mole alcohol. It ispreferred that the mole ratio of dialkyl carbonate:alcohol be about 2:1.The ratio of alkali metal alkoxide:dialkyl carbonate may vary from about0.1:1 up to about 1:1 with a preferred ratio of alkali metalalkoxide:dialkyl carbonate of 1:2 (mole ratio) being preferred.

The reaction temperature range may vary from about 50° C. up to about100° C. and the reaction pressure may vary from about atmosphericpressure up to about 10 atmospheres. Higher temperatures of reactionnecessitate higher pressures over the reaction mass in order to preventthe reaction product from evaporating therefrom.

During the reaction, the alkyl ester reaction product is continuouslyremoved as by using a Bidwell trap apparatus.

Examples of the reaction products prepared in accordance with theprocess of our invention and their organoleptic properties are asfollows:

                  TABLE I                                                         ______________________________________                                        Reaction Product                                                                           Perfume       Food Flavor                                        Structure    Properties    Properties                                         ______________________________________                                         ##STR69##   A woody, jasmine, floral, green, fruity, leathery, herbaceous                 , pine- apple-like aroma profile.                                                           A sweet, fruity, fresh pineapple aroma and                                    taste at 0.2 ppm.                                   ##STR70##   A floral, jasmine, fruity, sweet, grapefruit-like, leathery                   and coconut-like aroma profile.                                                             A sweet, grapefruit- like, coconut-like aroma                                 and taste profile at 0.1 ppm.                       ##STR71##   A floral (jasmine- like), green, fruity, mushroom- like                       aroma profile with intense mushroom-like and anisic-like                      under- tones. A green, mushroom, licorice-like, fruity aroma                                and taste profile at 0.05 ppm.                      ##STR72##   A floral, jasmine- like aroma.                                                              A tropical fruit taste at 0.1                      ______________________________________                                                                   ppm.                                           

An additional aspect of our invention is in the admixture of compoundshaving the structure: ##STR73## in combination with normethyl jasmonatehaving the structure: ##STR74## and methyl jasmonate having thestructure: ##STR75## The operable mole ratio of 1-hydroxymethyl-2-acylcyclopropane derivatives of our invention to methyl jasmonate ornormethyl jasmonate (mole ratios) is from 0.1:1 up to 1:0.1.

The 1-hydroxymethyl-2-acyl cyclopropane derivatives of our invention canbe used to contribute an intense, woody, jasmine, floral, green, fruity,sweet, herbaceous, pineapple-like, grapefruit-like, leathery,coconut-like, mushroom-like aroma with mushroom-like and anisic-likeundertones to perfumes, perfumed articles and colognes. (Samples ofperfumed articles are anionic, cationic, nonionic or zwitterionic solidor liquid detergents, fabric softeners including drier-added fabricsoftener articles and fabric softener compositions, perfumed polymersand shampoos.) As olfactory agents, the 1-hydroxymethyl-2-acylcyclopropane derivatives of our invention can be formulated into or usedas components of a "perfume composition" or can be used as components ofa "perfumed article" or the perfume composition may be added to"perfumed articles".

The term "perfume composition" is used herein to mean a mixture oforganic compounds including, for example, alcohols (other than thealcohols of our invention), aldehydes, ketones, nitriles, ethers,lactones, esters (other than the esters of our invention), carbonates(other than the carbonates of our invention), natural essential oils,synthetic essential oils and frequently hydrocarbons which are admixedso that the combined odors of the individual components produce apleasant or a desired fragrance. Such perfume compositions usuallycontain (a) the main note or "bouquet" or foundation stone of thecomposition; (b) modifiers which round off and accompany the main note;(c) fixatives which include odorous substances which lend a particularnote to the perfume throughout all stages of evaporation, and substanceswhich retard evaporation; and (d) topnotes which are usuallylow-boiling, fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, the individual compounds of this invention ormixtures thereof can be used taken alone or in combination withnormethyl jasmonate and methyl jasmonate to alter the aromacharacteristics of a perfume composition, for example, by highlightingor moderating the olfactory reaction contributed by another ingredientin the composition. The amount of the 1-hydroxymethyl-2-acylcyclopropane derivatives of this invention which will be effective inperfume compositions depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 0.5% of the1-hydroxymethyl-2-acyl cyclopropane derivatives of our invention or evenless, can be used to impart or augment interesting sweet, green,herbaceous, fruity, jasmine, floral, leathery, grapefruit-like,coconut-like and mushroom-like aromas with mushroom-like and anisicundertones to soaps, liquid and solid cationic, anionic, nonionic orzwitterionic detergents, cosmetic powders, liquid and solid fabricsofteners, drier-added fabric softener articles, optical brightenercompositions, perfumed polymers and other products. The amount employedcan range up to 50% or more and will depend on considerations of cost,nature of the end product and the effect desired on the finished productand particular fragrance sought.

The 1-hydroxymethyl-2-acyl cyclopropane derivatives of our invention canbe used alone or in a perfume composition as an olfactory component indetergents and soaps, space odorants and deodorants; perfumes; colognes,toilet water, bath salts; hair preparations such as lacquers, pomades,brilliantines and shampoos; cosmetic preparations such as creams,deodorants, hand lotions and sun screens; powders such as talcs, dustingpowders, face powders and the like. When used as an olfactory componentof a perfumed article such as a cationic, nonionic, anionic orzwitterionic solid or liquid detergent, as little as 0.01% of the1-hydroxymethyl-2-acyl cyclopropane derivatives will suffice to impartan interesting woody, jasmine, floral, green, leathery, fruity,herbaceous, pineapple-like, grapefruit-like, coconut-like andmushroom-like aroma with mushroom-like and anisic undertones. Generallyno more than 0.9% by weight of the perfumed article is required.Accordingly, the range of 1-hydroxymethyl-2-acyl cyclopropanederivatives in the perfumed article may vary from about 0.01% up toabout 0.9%.

In addition, the perfume composition can contain a vehicle or carrierfor the 1-hydroxymethyl-2-acyl cyclopropane derivatives alone or withother ingredients such as methyl jasmonate or normethyl jasmonate. Thevehicle can be a liquid such as a non-toxic alcohol such as ethanol, aglycol such as propylene glycol or the like. The carrier can be anabsorbent solid such as a gum such as gum arabic, guar gum or xanthangum or components for encapsulating the composition such as gelatinwhich can be used to form a capsule wall surrounding the perfume oil asby means of coacervation, or a urea formaldehyde prepolymer which can beused to form a polymeric urea formaldehyde wall surrounding the perfumeoil by means of polymerization.

In addition to its uses in perfumery, perfumed articles or colognes inaugmenting or enhancing the aroma of perfumes, perfumed articles andcolognes, the 1-hydroxymethyl-2-acyl cyclopropane derivatives of ourinvention can be used to augment or enhance the aroma or taste of otherconsumable materials including foodstuffs, chewing gums, toothpastes,medicinal products and chewing tobaccos.

When the 1-hydroxymethyl-2-acyl cyclopropane derivatives of ourinvention are used as food flavor adjuvants or medicinal product flavoradjuvants or toothpaste flavor adjuvants or chewing gum flavor adjuvantsor chewing tobacco flavor adjuvants, the nature of the co-ingredientsincluded with each of said 1-hydroxymethyl-2-acyl cyclopropanederivatives in formulating the product composition will also serve toaugment or enhance the organoleptic characteristics of the ultimatefoodstuff, chewing gum, medicinal product, toothpaste or chewing tobaccotreated therewith.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is required that any suchmaterial be "ingestibly acceptable", and thus non-toxic or otherwisenon-deleterious, particularly from an organoleptic standpoint wherebythe ultimate flavor and/or aroma of the consumable material used doesnot cause the consumable material to have unacceptable aroma and tastenuances.

It is a further requirement that such material be organolepticallycompatible with the foodstuff with which it is used so that the flavorand aroma nuances of such material, taken together with the flavor andaroma nuances of the foodstuff (as a whole) give rise to a harmoniouslyaesthetically pleasing aroma and taste profile. Such materials, ingeneral, may be characterized as flavoring adjuvants or vehiclescomprising broadly, stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g. sodium chloride,antioxidants, e.g. calcium and sodium ascorbate, ascorbic acid,butylated hydroxy-anisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxytoluene(2,6-ditertiary-butyl-4-methyl phenol), propyl gallate and thelike and seqestrants, e.g. citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g. agar agar,carrageenan, cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth, gelatin, proteinaceous materials, lipids,carbohydrates, starches, pectins and emulsifiers, e.g. mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g. sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g. fatty acids suchas palmitic acid, myristic acid and the like, mono- and diglycerides offatty acids, lecithin, defoaming and flavor-dispensing agents such assorbitan, monostearate, potassium monostearate, hydrogenated tallowalcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g. benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like,starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g. sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like,colorants, e.g. carminic acid, cochineal, tumeric, curcumin and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g. aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g. calcium lactate and calcium sulfate; nutrient supplements, e.g.iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, 2-methyl-cis-3-pentenoic acid; ketones andaldehydes, e.g. octanal, n-decanal, acetaldehyde, acetophenone, acetone,acetyl methyl carbinol, acrolein, n-butanal, crotonal, diacetyl,2-methyl butanal, beta,betadimethyl-acrolein, methyl-n-amyl ketone,n-hexanal, 2-hexenal, isopentanal, hydrocinnamic aldehyde,cis-3-hexenal, 2-heptenal, nonyl aldehyde, citral,4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,2-methyl-3-butanone, benzaldehyde, damascone, damascenone, acetophenone,2-heptanone, o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-octanone,2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, furfural, 2-methyl furfural, cinnamaldehyde,beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcoholssuch as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol,ethanol, geraniol, 1-hexanol, 2-heptanol, trans-2-hexenol-1,cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten- 3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, fenchyl alcohol, isofenchylalcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate,eugenol, linalook, 2-heptanol, acetoin; esters such as butyl acetate,ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate,dimethylanthranilate, methyl acetate, methyl butyrate, methyl caproate,methyl isobutyrate, alpha-methylphenylglycidate, ethyl succinate,isobutyl cinnamate, cinnamyl formate, methyl cinnamate and terpinenylacetate; hydrocarbons such as dimethyl naphthalene, dodecane, methyldiphenyl, methyl naphthalene, myrcene, cadinene, limonene, naphthalene,octadecane, tetradecane, tetramethyl naphthalene, tridecane, trimethylnaphthalene, undecane, caryophyllene, 1-phellandrene, p-cymene,1-alpha-pinene; pyrazines such as 2,3-dimethylpyrazine,2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethyl-pyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine,alpha-methyl-3-ethylpyrazine, tetramethylpyrazine, trimethylpyrazine;essential oils such as jasmine absolute, cassia oil, cinnamon bark oil,rose absolute, orris absolute, lemon essential oil, orange essentialoil, grapefruit essential oil, Bulgarian rose, yara yara and vanilla;lactones such as gammanonalactone; sulfides, e.g. methyl sulfide andother materials such as maltol and acetals (e.g. 1,1-diethoxyethane,1,1-dimethoxyethane and dimethoxymethane).

The specific flavoring adjuvants selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e. foodstuff, whether simulated or natural, and should, in any event,(1) be organoleptically compatible with the 1-hydroxymethyl-2-acylcyclopropane derivatives of our invention by not covering or spoilingthe organoleptic properties (aroma and/or taste) thereof; (2) benon-reactive with the 1-hydroxymethyl-2-acyl cyclopropane derivatives ofour invention; and (3) be capable of providing an environment in whichthe 1-hydroxymethyl-2-acyl cyclopropane derivatives can be dispersed oradmixed to provide a homogeneous medium. In addition, selection of oneor more flavoring adjuvants, as well as the quantities thereof willdepend upon the precise organoleptic character desired in the finishedproduct. Thus, in the case of flavoring compositions, ingredientselection will vary in accordance with the foodstuff, chewing gum,medicinal product or toothpaste to which the flavor and/or aroma are tobe imparted, modified, augmented or enhanced. In contradistinction, inthe preparation of solid products, e.g. simulated foodstuffs,ingredients capable of providing normally solid compositions should beselected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of1-hydroxymethyl-2-acyl cyclopropane derivatives employed in a particularinstance can vary over a relatively wide range, depending upon thedesired organoleptic effects to be achieved. Thus, correspondinglygreater amounts would be necessary in those instances wherein theultimate food composition to be flavored is relatively bland to thetaste, whereas relatively minor quantities may suffice for purposes ofenhancing the composition merely deficient in natural flavor or aroma.The primary requirement is that the amount selected be effective, i.e.sufficient to augment or enhance the organoleptic characteristics of theparent composition, whether foodstuff per se, chewing gum per se,medicinal product per se, toothpaste per se, or flavoring composition.

The use of insufficient quantities of 1-hydroxymethyl-2-acylcyclopropane derivatives will, of course, substantially vitiate anypossibility of obtaining the desired results while excess quantitiesprove needlessly costly and, in extreme cases, may disrupt theflavor-aroma balance, thus proving self-defeating. Accordingly, theterminology "effective amount" and "sufficient amount" is to be accordeda significance in the context of the present invention consistent withthe obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of 1-hydroxymethyl-2-acylcyclopropane derivatives ranging from a small but effective amount, e.g.0.02 parts per million (ppm) up to about 50 parts per million (ppm)based on total composition are suitable. Concentrations in excess of themaximum quantity stated are not normally recommended, since they fail toprovide commensurate enhancement of organoleptic properties. In thoseinstances where the 1-hydroxymethyl-2-acyl cyclopropane derivatives areadded to the foodstuff as an integral component of a flavoringcomposition, it is, of course, essential that the total quantity offlavoring composition employed be sufficient to yield an effective1-hydroxymethyl-2-acyl cyclopropane derivative concentration in thefoodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the 1-hydroxymethyl-2-acyl cyclopropanederivatives in concentrations ranging from about 0.05% up to about 5% byweight based on the total weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the 1-hydroxymethyl-2-acyl cyclopropanederivatives of our invention with, for example, gum arabic, gumtragacanth, carrageenan and the like, and thereafter spray-drying theresultant mixture whereby to obtain the particulate solid product.Pre-prepared flavor mixes in powder form, e.g. a fruit-flavored powdermix is obtained by mixing the dried solid components, e.g. starch, sugarand the like and the 1-hydroxymethyl-2-acyl cyclopropane derivatives ina dry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the 1-hydroxymethyl-2-acylcyclopropane derivatives of our invention the following adjuvants:

bergamot oil;

citral;

amyl alcohol;

ethyl acetate;

5-phenyl-4-pentenal;

5-phenyl-2-pentenal;

n-octanal;

n-decanal;

limonene;

geraniol;

cadinene;

dimethylanthranilate;

vanillin;

amyl butyrate;

2-(n-pentyl)-thiazole;

2-(i-butyl)-thiazole;

2-(i-propyl)-thiazole;

2-(n-propyl)-thiazole;

the dimethyl acetal of 2-phenyl-4-pentenal;

methional;

4-methylthiobutanal;

2-ethyl-3-acetyl pyrazine;

tetramethyl pyrazine;

2-methyl pyrazine;

2-trans hexenal;

maltol;

2-phenyl-4-pentenal;

2-phenyl-4-pentenal dimethyl acetal; and

2-phenyl-4-pentenal diethyl acetal.

The following examples are intended to illustrate the instant invention.It will be understood that these examples are illustrative and that theinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I Reaction of 2,4-decanedione with Epichlorohydrin

Reaction: ##STR76##

Into a 1-liter reaction flask equipped with stirrer, reflux condenser,thermometer, addition funnel and nitrogen atmosphere blanket apparatusand Bidwell trap is placed 240 ml isopropyl alcohol. With stirring, 130grams (2.4 moles) of sodium methoxide is added to the reaction masswhile maintaining the reaction mass temperature at 24°-42° C. Anadditional 100 ml of isopropyl alcohol is then added and the reactionmass is heated to reflux. While refluxing and over a period of 1 hour,at a temperature of 78°-93° C., 204 grams (1.2 moles) of 2,4-decanedioneis added to the reaction mass.

While maintaining the reaction mass at 66°-80° C. over a period of 1hour, 111 grams (1.2 moles) of epichlorohydrin is added to the reactionmass. The reaction mass with stirring is then heated for a period of 3hours at 66°-80° C. During the addition of the epichlorohydrin, thereaction product is trapped in the Bidwell trap.

The reaction mass is then quenched with 15% aqueous hydrochloric acid,then washed with one 500 ml portion of water followed by four 500 mlportions of saturated sodium chloride.

FIG. 1 is the GLC profile for the resulting reaction product.(Conditions: 6'×0.25" 10% SF-96 column programmed at 100°-220° C. at 8°C. per minute). The peak indicated by reference numeral "10" is the peakfor the side product having the structure: ##STR77## wherein Y₁ and Y₂are the same or different and each represents chloro or hydroxyl. Thepeak indicated by reference numeral "11" is the peak for the actualproduct having the structure: ##STR78##

A portion of the reaction product is distilled on a spinning bandcolumn. Fraction 12 of the distillation product is analyzed via GLC(conditions: 10% SF-96 8'×1/4" column programmed at 100°-220° C. at 8°C. per minute). FIG. 1A is the GLC profile for this distillationproduct. The peak indicated by reference numeral "12" is the peak forthe compound having the structure: ##STR79## The peak indicated byreference numeral "13" is the peak for the compound having thestructure: ##STR80##

FIG. 2 is the NMR spectrum for the compound of peak 10 of FIG. 1containing the compound having the structure: ##STR81## (Solvent: CFCl₃; Field strength: 100 MHz).

FIG. 3 is the infra-red spectrum for the peak indicated by referencenumeral "10" of FIG. 1 for the compound having the structure: ##STR82##

FIG. 3A is the NMR spectrum for the peak indicated by reference numeral"12" on FIG. 1A, having the structure: ##STR83## (Solvent: CFCl₃ ; Fieldstrength: 100 MHz).

FIG. 3B is the infra-red spectrum for the peak indicated by referencenumeral "12" on FIG. 1A for the compound having the structure: ##STR84##

EXAMPLE II Reaction of Dimethyl Carbonate and Alcohol of Example I

Reaction: ##STR85##

Into a 1 liter reaction flask equipped with addition funnel, heatingmantle, nitrogen blanket apparatus and Bidwell trap is placed 38.6 grams(0.7 moles) of sodium methoxide and 126 grams (1.4 moles) of dimethylcarbonate. The resulting mixture is heated to reflux and while refluxingat a temperature of between 69° and 86° C., over a period of 1 hour, thealcohol produced according to Example I having the structure: ##STR86##is added to the reaction mass, dropwise (while taking off methyl alcoholusing the Bidwell trap). The reaction mass is then continued to berefluxed for 15 minutes. At the end of the 15 minute period, 126 gramsof new dimethyl carbonate is added to the reaction mass and additionalmethyl alcohol is removed via the Bidwell trap. The reaction mass isthen heated for an additional 5 hours at 79°-86° C.

At the end of the reaction, the reaction mass is quenched with 17%aqueous hydrochloric acid to a pH of 2. The reaction mass is then washedwith water to a neutral pH and then washed with three 500 ml volumes ofwater.

The resulting product has the structure: ##STR87##

FIG. 4 is the GLC profile for the reaction product (conditions: 10%SF-96 column, 6'×0.25" programmed at 100°-220° C. at 8° C. per minute).The peak indicated by reference numeral "40" is the peak for thecompound defined according to the structure: ##STR88##

FIG. 5 is the NMR spectrum for the peak indicated by reference numeral"40" of FIG. 4 for the compound having the structure: ##STR89##(Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 6 is the infra-red spectrum for the peak indicated by referencenumeral "40" of FIG. 4 for the compound having the structure: ##STR90##

EXAMPLE III Preparation of Acetic Acid Ester "Intermediate"

Reaction: ##STR91##

Into a 1 liter reaction flask equipped with stirrer, reflux condenser,addition funnel, Bidwell trap and nitrogen atmosphere blanket apparatusis placed 250 ml toluene and 130 grams of sodium methoxide (2.4 moles).The reaction mass is heated to reflux and while refluxing andmaintaining the temperature at 92°-117° C. over a period of 1.5 hours,2,4-decanedione (217 grams; 1.2 moles) is added to the reaction mass.

Then, over a period of 1.5 hours while maintaining the temperature at103°-117° C. with stirring, 111 grams (1.2 moles) of epichlorohydrin isadded to the reaction mass. The reaction mass is then heated for anadditional 4 hours at 110°-113° C. while removing water of reaction viathe Bidwell trap.

The reaction mass is then quenched with 37% hydrochloric acid to a pH of2. The reaction mass is then transferred to a separatory funnel andwashed with 3 one-liter portions of water followed by one 1-literportion of saturated sodium chloride solution.

The resulting product is then distilled on a 2" Splash column packedwith stones yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     Pressure                                                                             Fraction                                   Number    (°C.)                                                                          (°C.)                                                                            mm/Hg. (grams)                                    ______________________________________                                        1         35/57   44/77     10/10  853                                        2         75      127       53     364                                        3         75      118       6       35                                        4         130     173       3      362                                        5         54      220       3      189                                        ______________________________________                                    

Fractions 4 and 5 of the 2" Splash column distillation are bulked andre-distilled on a 1' Goodloe column (1" in diameter) yielding thefollowing fractions:

    ______________________________________                                                Vapor     Liquid            Weight of                                 Fraction                                                                              Temp.     Temp.     Pressure                                                                              Fraction                                  Number  (°C.)                                                                            (°C.)                                                                            mm/Hg   (grams)                                   ______________________________________                                        1       50/95     101/144   76/5    43.0                                      2        88       136       22       3.0                                      3       81/92     124/142   11/1    19.5                                      4        97       144       1       19.5                                      5       101       148       1       18.5                                      6       108       152       1       21.5                                      7       110       155       1       43.0                                      8       100       168       1       50.0                                      9       143       200       1       52.5                                      10      127/118   108/20    0.8/07  --                                        11      145       225       0.7     --                                        12      146       240       0.7     22.0                                      ______________________________________                                    

The resulting reaction product has the structure: ##STR92##

FIG. 7 is the GLC profile for the reaction product (conditions: 6'×0.25"10% SF-96 column programmed at 100°-220° C. at 8° C. per minute). Thepeak indicated by reference numeral "70" is the peak for the reactionproduct having the structure: ##STR93##

FIG. 8 is the NMR spectrum for the compound having the structure:##STR94## of the peak indicated by reference numeral "70" of FIG. 7(Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 9 is the infra-red spectrum for the peak indicated by referencenumeral "70" of FIG. 7 for the compound having the structure: ##STR95##

EXAMPLE IV Jasmine Perfume Formulations

The following mixtures are prepared:

    ______________________________________                                                           Parts by Weight                                                                 Ex-     Ex-     Ex-                                                           ample   ample   ample                                    Ingredients          IV(A)   IV(B)   IV(C)                                    ______________________________________                                        Para cresol          1       1       1                                        Acetyl methyl anthranilate                                                                         20      20      20                                       Farnesol             4       4       4                                        Cis-3-hexenyl benzoate                                                                             30      30      30                                       Nerolidol            30      30      30                                       Indol                15      15      15                                       Eugenol              20      20      20                                       Benzyl alcohol       40      40      40                                       Methyl linoleate     40      40      40                                       Jasmine lactone      20      20      20                                       Dihydromethyl jasmonate                                                                            10      10      10                                       Linalool             150     150     150                                      Benzyl acetate       400     400     400                                      Abietyl alcohol      150     150     150                                      Compound prepared according to                                                Example I having the structure:                                                ##STR96##           20      0       0                                         Compound prepared according to                                               Example II having the structure:                                               ##STR97##           0       20      0                                         Compound prepared according to                                               Example III having the structure:                                              ##STR98##           0       0       20                                       ______________________________________                                    

Each of the 1-hydroxymethyl-2-acyl cyclopropane derivatives having thestructures: ##STR99## contributes an intense, natural jasmine-likenuance to this jasmine formulation. The compound having the structure:##STR100## contributes a woody, jasmine-like, floral, green, fruity,leathery and pineapple-like aroma nuance.

The compound having the structure: ##STR101## contributes to thisjasmine formulation a floral, jasmine, fruity, sweet, grapefruit-like,leathery and coconut-like aroma profile.

The compound having the structure: ##STR102## imparts to this jasmineformulation an interesting floral, green, fruity, mushroom-like aromawith anisic undertones.

The combination of cis-jasmone and normethyl jasmonate in ratios of from1:9 up to 9:1 of cis-jasmone or normethyl jasmonate:one of the1-hydroxymethyl-2-acyl cyclopropane derivatives of our invention impartsa very interesting natural jasmine aroma to this perfume formulation aswell as other perfume formulations encompassed by our invention.

EXAMPLE V Preparation of Cosmetic Powder Compositions

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table II below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table II below.

                  TABLE II                                                        ______________________________________                                        Substance        Aroma Description                                            ______________________________________                                         ##STR103##      A woody, jasmine, floral, green, fruity, leathery,                            herbaceous, pineapple-like aroma profile.                     ##STR104##      A floral, jasmine, fruity, sweet, grapefruit-like,                            leathery and coconut-like aroma profile.                      ##STR105##      A floral (jasmine-like), green, fruity, mushroom-like                         aroma profile with intense mushroom-like and anisic-like                      ndertones.                                                    ##STR106##      A floral, jasmine-like aroma.                                 Perfume composition of                                                                        An intense jasmine aroma                                     Example IV(A)    with pleasant woody, floral,                                                  green, fruity, leathery and                                                   pineapple-like undertones.                                   Perfume composition of                                                                         A jasmine aroma with floral,                                 Example IV(B)    fruity, sweet, grapefruit-                                                    like, leathery and coconut-                                                   like undertones.                                             Perfume composition of                                                                         A jasmine aroma with floral,                                 Example IV(C)    mushroom-like, green,                                                         fruity and anisic-like                                                        undertones.                                                  ______________________________________                                    

EXAMPLE VI Perfumed Liquid Detergents

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976 incorporated by reference herein) with aroma nuances asset forth in Table II of Example V, are prepared containing 0.10%,0.15%, 0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in TableII of Example V. They are prepared by adding and homogeneously mixingthe appropriate quantity of substance set forth in Table II of Example Vin the liquid detergent. The detergents all possess excellent aromas asset forth in Table II of Example V, the intensity increasing withgreater concentrations of substance as set forth in Table II of ExampleV.

EXAMPLE VII Preparation of Colognes and Handkerchief Perfumes

Compositions as set forth in Table II of Example V are incorporated intocolognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions; andinto handkerchief perfumes at concentrations of 15%, 20%, 25% and 30%(in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table II ofExample V are imparted to the colognes and to the handkerchief perfumesat all levels indicated.

EXAMPLE VIII Preparation of Soap Compositions

One hundred grams of soap chips (per sample) (IVORY® produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table II of Example V untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of three hours and the resulting liquids are placed intosoap molds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table II of Example V.

EXAMPLE IX Preparation of Solid Detergent Compositions

Detergents are prepared using the following ingredients according toExample I of Canadian Pat. No. 1,007,948 (incorporated by referenceherein):

    ______________________________________                                        Ingredient         Percent by Weight                                          ______________________________________                                        "Neodol ® 45-11" (a C.sub.14 -C.sub.15                                                       12                                                         alcohol ethoxylanted with                                                     11 moles of ethylene oxide)                                                   Sodium carbonate   55                                                         Sodium citrate     20                                                         Sodium sulfate, water                                                                            q.s.                                                       brighteners                                                                   ______________________________________                                    

This detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table II of Example V. Each ofthe detergent samples has an excellent aroma as indicated in Table II ofExample V.

EXAMPLE X

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated herein by reference),nonwoven cloth substrates useful as drier-added fabric softeningarticles of manufacture are prepared wherein the substrate, thesubstrate coating, the outer coating and the perfuming material are asfollows:

1. A water "dissolvable" paper ("Dissolvo Paper")

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. An outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the substances as set forth in Table II of Example V,supra.

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table II of Example V, supra, consist of a substrate coating having aweight of about 3 grams per 100 square inches of substrate; a firstcoating located directly on the substrate coating consisting of about1.85 grams per 100 square inches of substrate; and an outer coatingcoated on the first coating consisting of about 1.4 grams per 100 squareinches of substrate. One of the substances of Table II of Example V,supra, is admixed in each case with the outer coating mixture, therebyproviding a total aromatized outer coating weight ratio to substrate ofabout 0.5:1 by weight of the substrate. The aroma characteristics areimparted in a pleasant manner to the head space in a dryer on operationthereof in each case using said dryer-added fabric softener non-wovenfabric and these aroma characteristics are described in Table II ofExample V, supra.

EXAMPLE XI Hair Spray Formulations

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 copolymer manufactured by the GAF Corporation of 140 West51st Street, New York, N.Y., in 91.62 grams of 95% food grade ethanol.8.0 grams of the polymer is dissolved in the alcohol. The followingingredients are added to the PVP/VA alcoholic solution:

    ______________________________________                                            Dioctyl sebacate         0.05 weight percent                                  Benzeyl alcohol          0.10 weight percent                                  Dow Corning 473 fluid    0.10 weight percent                                  prepared by the Dow Corning                                                   Corporation                                                                   Tween 20 surfactant      0.03 weight percent                                  prepared by ICI America                                                       Corporation                                                                   One of the perfumery     0.10 weight percent                                  substances as set forth                                                       in Table II of Example V,                                                     supra                                                                     ______________________________________                                    

The perfuming substances as set forth in Table II of Example V, supra,add aroma characteristics as set forth in Table II of Example V, supra,which are rather intense and esthetically pleasing to the users of thesoft-feel, good-hold pump hair sprays.

EXAMPLE XII Conditioning Shampoos

Monamid CMA (prepared by the Mona Industries Company) (3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Proctor & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation) (1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.). This material is COMPOSITION A.

Gafquat®755N polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weightpercent sodium sulfite and 1.4 weight percent polyethylene glycol 6000disterate produced by Armak Corporation. This material is COMPOSITION B.

The resulting COMPOSITION A and COMPOSITION B are then mixed in a 50:50wt ratio of A:B and cooled to 45° C. and 0.3 wt percent of perfumingsubstance as set forth in Table II of Example V added to the mixture.The resulting mixture is cooled to 40° C. and blending is carried outfor an additional one hour in each case. At the end of this blendingperiod, the resulting material has a pleasant fragrance as indicated inTable II of Example V.

EXAMPLE XIII Grapefruit Formulation

The following formulation is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Grapefruit oil        92.0                                                    Bergamot oil          2.0                                                     Citral                3.0                                                     Amyl alcohol          1.0                                                     Ethyl acetate         1.0                                                     5-Phenyl-4-pentenal   1.0                                                     3-Mercapto-4-heptanol 0.5                                                     Compound having the structure:                                                                      0.5                                                      ##STR107##                                                                    prepared according to Example II                                             ______________________________________                                    

When the above grapefruit formulation is added to water at the rate of1%, an excellent grapefruit drink is prepared. The compound having thestructure: ##STR108## prepared according to Example II given an intense,citrusy note to the instant formulation with pleasant, coconut-likenuances thereby rendering it more desirable and tropical fruit-like. Theeffect rendered by the compound having the structure: ##STR109## isenhanced by adding 0.02 parts by weight of the compound having thestructure: ##STR110## which imparts a pleasant pineapple-like nuance tothis formulation.

EXAMPLE XIV Vegetable Flavor Formulation

The compound having the structure: ##STR111## is added directly to afood product prior to processing and canning. The following illustratesthe beneficial flavor effect when the compound having the structure:##STR112## prepared according to Example III is added directly toseveral products just prior to their consumption:

i. blended vegetable sauce containing mushrooms at approximately 30 ppm,brings out the boiled mushroom nuanes.

ii. in vegetable soup at 40 ppm, imparts a fresh vegetable flavor withmushroom nuances. The green notes give the entire vegetable flavor afuller body.

iii. in bean tomato sauce at approximately 20 ppm, modifies the flavorby reducing the harsh character of the tomato space mixture while at thesame time adding green fresh notes and developing the "cooked" tomatonote to a "fresh" tomato note. Also adds mushroom nuances to the sauce.

EXAMPLE XV Vegetarian Vegetable Soup

The compound defined according to the structure: ##STR113## is added atthe rate of 2 ppm to condensed vegetarian vegetable soup (Shop Rite®brand). One liter of water is added to one liter of soup and thoroughlyadmixed. The resulting mixture is then simmered (200° F.) for a periodof 10 minutes. The resulting soup is compared by a bench panel with asoup which has no compound defined according to the structure:##STR114## added thereto. The soup containing the compound having thestructure: ##STR115## added thereto is unanimously preferred as having amore vegetable-like taste with mushroom nuances with fuller mouth feeland better aroma and, in addition, a pleasant slight, green nuance.

EXAMPLE XVI A. Powder Form

Twenty grams of the flavor composition of Example XIII which flavorcomposition contains the compound having the structure: ##STR116## isemulsified in a solution containing 300 grams gum acacia with 700 gramsof water. The emulsion is spray-dried with a Bowen Lab Model drierutilizing 250 c.f.m. of air with an inlet temperature of 500° F. andoutlet temperature of 200° F. and a wheel speed of 50,000 r.p.m.

B. Paste Blend

    ______________________________________                                        The following mixture is then prepared:                                       Ingredients             Parts by Weight                                       ______________________________________                                        Liquid flavor composition of                                                                          48.4                                                  Example XIII                                                                      Cab-O-Sil M-5                3.2                                              (Brand of silica produced by the                                              Cabot Corporation of 125 High                                                 Street, Boston, Mass. 02110);                                                 Physical properties:                                                          Surface area: 200 m.sup.2 /gm.                                                Nominal particle size: 0.012 microns                                          Density: 2/3 lbs/cu. ft.                                                  ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid flavor composition withvigorous stirring, thereby resulting in a viscous liquid. 48.4 parts byweight of the powder flavor composition prepared in Part A is thenblended into said viscous liquid, with stirring at 25° C. for a periodof 30 minutes, resulting in a thixotropic sustained release flavorpaste.

EXAMPLE XVII Chewing Gum

100 parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XVI. 300 parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BankerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant long-lastinggrapefruit flavor.

EXAMPLE XVIII Toothpaste Formulation

The following separate groups of ingredients are prepared:

    ______________________________________                                        Group "A"                                                                     30.200        Glycerine                                                       15.325        Distilled water                                                  0.100        Sodium benzoate                                                  0.125        Saccharin sodium                                                 0.400        Stannous fluoride                                               Group "B"                                                                     12.500        Calcium carbonate                                               37.200        Dicalcium phosphate (dihydrate)                                 Group "C"                                                                      2.000        Sodium n-lauroyl sarcosinate                                                  (foaming agent)                                                 Group "D"                                                                      1.200        Flavor material of XVI                                          100.000       Total                                                           ______________________________________                                    

Procedure:

1. To ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly, the sodiumn-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste when used in a normal tooth-brushing procedureyields a pleasant graepfruit flavor of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE XIX Chewable Vitamin Tablets

The flavor material produced according to the process of Example XVI isadded to a chewable vitamin tablet formulation at a rate of 5 gm/kgwhich chewable vitamin tablet formulation is prepared as follows:

    ______________________________________                                        Ingredients            Gms/1000 Tablets                                       ______________________________________                                        Vitamin C (ascorbic acid) as                                                                         70.000                                                 ascorbic acid solution mixture 1:1)                                           Vitamin B.sub.1 (thiamine mononitrate) as                                                            4.000                                                  Rocoat ® thiamine mononitrate 33%                                         (Hoffman LaRoche)                                                             Vitamin B.sub.2 (riboflavin) as Rocoat ®                                                         5.000                                                  riboflav:n 331/3%                                                             Vitamin B.sub.6 (pyridoxine hydrochloride)                                                           4.000                                                  as Rocoat ® pyridoxide hydrochloride                                      331/3%                                                                        Niacinamide as Rocoat ® niacinamide                                                              33.000                                                 331/3%                                                                        Calcium pantothenate   11.500                                                 Vitamin B.sub.12 (cyanocobalamin) as                                                                 3.500                                                  Merck 0.1% in gelatin                                                         Vitamin E (dl-alpha tocophenyl acetate as                                                            6.600                                                  dry Vitamin E acetate 331/3% Roche                                            d-Biotin               0.044                                                  Certified lake color   5.000                                                  Flavor of Example XVI  5.000                                                  Sweetener-sodium saccharin                                                                           1.000                                                  Magnesium stearate lubricant                                                                         10.000                                                 Mannitol q.s. to make  500.000                                                ______________________________________                                    

Preliminary tablets are prepared by slugging with flat faced punches andgrinding the slugs to 14 mesh. 13.5 grams dry Vitamin A acetate and 0.6grams Vitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 grams each.

Chewing of the resultant tablet yields a pleasant, long-lasting,consistently strong grapefruit flavor for a period of 12 minutes.

EXAMPLE XX Guava Nectar Formulation

To commercial guava nectar at the rate of 0.2 ppm is added the compoundhaving the structure: ##STR117## prepared according to Example I. Thecompound having the structure: ##STR118## adds to the guava nectar avery natural tropical fruit aroma and taste nuance which causes it to bereminiscent of fresh guava.

What is claimed is:
 1. The 1-hydroxymethyl-2-acyl cyclopropanederivative having the structure: ##STR119##
 2. The1-hydroxymethyl-2-acyl cyclopropane derivative having the structure:##STR120##
 3. The 1-hydroxymethyl-2-acyl cyclopropane derivative havingthe structure: ##STR121##